BRPI0116758B1 - Naphthopyran Compound and Photochromic Article - Google Patents

Description

"NAFTOPYRANE COMPOUND AND PHOTOCHROME ARTICLE" Cross Reference to Related Patent Applications [0001] This patent application claims the priority of U.S. Provisional Patent Application Serial Number 60 / 258,973, filed December 29, 2000. [ The present invention relates to certain novel naphthopyran compounds. More particularly, the present invention relates to novel photochromic indene-fused naphthopyran compounds and to compositions and articles containing such novel naphthopyran compounds. When exposed to light radiation containing ultraviolet rays, such as ultraviolet radiation found in sunlight or light from a mercury lamp, various photochromic compounds exhibit a reversible color change. When the ultraviolet radiation is interrupted, said photochromic compound returns to its original color or colorless state. Several classes of photochromic compounds have already been synthesized and suggested for use in applications where a sunlight-induced reversible change or darkening is desired. U.S. Patent No. 3,567,605 (Becker) discloses a series of pyran derivatives, including certain benzopyran and naphthopyran. These compounds are described as chromene derivatives and are reported to undergo a color change, for example from colorless to orange-yellow, on ultraviolet light irradiation at temperatures below approximately 30 ° C. Irradiation of the compounds with visible light or when the temperature is raised above approximately 0 ° C is reported as reversing color to a colorless state. U.S. Patent No. 5,066,818 describes various 3,3-diaryl-3H-naphtho [2,1-b] pyranes as having desirable photochromic properties, for example, high staining activity and acceptable fading, for ophthalmic applications and other applications. Also disclosed by way of a comparative example in US Patent No. 5,066,818 isomeric 2,2-diaryl-2H-naphtho [1,2-b] pyranes, which are reported to require unacceptable long periods of time. to fade after activation. U.S. Patent No. 3,627,690 discloses 2,2-di-substituted-2H-naphtho [1,2-b] pyran photochromic compositions containing minimal amounts of either a base or a low-potency acid. para-moderate. The addition of both a base and an acid to the naphthopyran composition is reported to increase the fading rate of colored naphthopyran, thus maintaining them as useful in eye protection applications such as sun goggles. It is further reported that the fading rate of 2H-naphtho- [1,2-b] pyranes without the above mentioned additives ranges from several hours to several days to achieve full reversal. Indenonaptopyrans are known and have been disclosed in U.S. Pat. 5,645,767. 5,698,141. 5,723,072. 6,113,814 and 6,146,554 and in International Patent Application Publication No. WO 99/15518. In each of these disclosures, the indene group is in a reverse position compared to the indenonaptopyran of the present invention. Unexamined Japanese patent application P2000-327675A discloses an indenaphtopyran in which the indene group is substituted with fluorenyl. [0007] The present invention relates to a naphthopyran with a 2H-naphtho [1,2-b] pyran structure characterized in that it has a substituted or unsubstituted indene group fused at positions 2, 3 of the group next to naphthopyran . The compounds also have substituents at the 3-position of the pyran ring. It has unexpectedly been found that these compounds demonstrate a batochromic wavelength switching in the visible spectrum in which the maximum absorption of the activated (color) activated form of the photochromic compound, for example, the maximum lambda (Vis), occurs, thus resulting in varying activated colors. from yellow / brown to blue / gray. Due to batochromic switching, the compounds of the present invention demonstrate different colors from similar compounds without the unsubstituted or substituted indene group fused at positions 2, 3 of the side-group 1 of naphthopyran. In addition, the compounds of the present invention have demonstrated a high molar absorbance (or molar extinction coefficient) in UV, an acceptable fade rate without the addition of acids or bases, a high activated intensity, and a high coloration rate. Detailed Description of the Invention In recent years, photochromic plastic materials, particularly plastic materials for optical applications, have been the subject of considerable attention. In particular, plastic ophthalmic photochromic lenses have been investigated because of the weight advantage they offer vis-à-vis glass lenses. Further, photochromic transparencies for vehicles, such as cars and airplanes, have been of interest because of the potential safety features that such transparencies offer. Except in the operating examples, or where otherwise indicated, all values, such as those expressing wavelength, ingredient amounts, variations or reaction conditions, used in this description and the claims. Accompanying persons are understood to be modified in all instances by the term "approximately" which means close to or near. As used herein, the terms "halo" and "halogen" are defined to include chlorine, fluoro, bromine and iodine and chlorine, fluorine, bromine, and iodine respectively. The term "aryl" is defined herein to include phenyl and naphthyl. The disclosures of the patents and articles cited herein describing the photochromic imbibition processes and compositions, the procedures for making the polymerizable and non-polymerizable compounds of the present invention, the complementary photochromic compounds, the polymeric coatings and methods of application. of such coatings, a host organic polymeric material and polymerised articles are incorporated herein by reference. In accordance with the present invention, it has now been discovered that innovative 2H-naphtho [1,2-b] pyran structures which have an unsubstituted or substituted indene group fused at positions 2, 3 of the next group 1 Naftopyrane and demonstrating activated colors ranging from yellow / orange to blue / gray, an acceptable fade rate, high activated intensity and a high coloration rate can be prepared. These compounds may be described as indeno [3 ', 2': 3,4] naphtho [1,2-b] pyran having 3-position substituents on the pyran ring. The substituents may also be present on carbon atoms numbers 5, 6, 7, 8, 9, 10, 11, 12, or 13 of the compounds. The indene group may be represented by the formula I 'in which the numbers from 1 to 9 represent the ring atoms of the indene group. A typical structure of 2H-naphtho [1,2-b] pyran is represented by the following formula I ", in which the letters a through n represent the sides and X represents the potential substituents known in the art. The compounds of the present invention may be represented by the following graphic formula I wherein the letters a through n represent the sides of the indenaphtopyran ring, and the numbers represent the ring atom numbers of the indenaphotopyran. The invention is a naphthalopyran compound of the structure 2H-naphtho [1,2-b] pyran as represented by formula I ", characterized in that it has fused to the side 1 of 2H-naphthalopyran a group represented by the graphic formula 1 ' at positions 2, 3 of group I '. The group represented by the formula 1 'may be unsubstituted such as when R1 and R2 are each hydrogen and equal to 0 or may be substituted with substituents known in the art for use in photochromic compounds. Different embodiments of the compounds of the present invention are contemplated based on photochromic activity. In the formula I ', R1 and R2 may each be selected from the group consisting of: (i) hydrogen, hydroxy, amine, mono- and disubstituted amine, C1-C6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 7 cycloalkyl, allyl, benzyl, monosubstituted benzyl, halogen and the group -C (0) W, wherein W is hydroxy, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 3 -C 7 cycloalkyloxy, phenyl, mono-substituted phenyl, phenoxy, amine, mono (C1-C6) alkylamine, di (C1-C6) alkylamine, morpholine, piperidine or pyrrolidyl, said amine substituents being selected from the group consisting of Cl - C6 alkyl, phenyl, benzyl and naphthyl, said benzyl and phenyl substituents being C1-C6 alkyl, C1-C6 alkoxy, piperidine, morpholine, di (C1-C6) alkylamine or fluoro; (Ü) unsubstituted, mono- and tri-substituted members selected from the group consisting of phenyl, naphthyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl, benzofuranyl, thienyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, and indolyl, said substituent groups being selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy, morpholine, piperidine, pyrrolidine, amine, mono- and disubstituted amine, said amine substituents being selected from the group consisting of C1-C6 alkyl, phenyl, benzyl and naphthyl; (Ii) mono-substituted phenyl having a substituent at the position for which it is a linking group, - (CH2) t- or -0- (CH2) t- where t is an integer 1, 2, 3, 4, 5 or 6, connected to an aryl group which is a member of another photochromic naphthalopyran; (Iv) a group, -OR5, wherein R5 is C1-C6 alkyl, C1-C6 acyl, phenyl (C1-C3) alkyl, mono (C1-C6) alkyl substituted phenyl (C1-C3) alkyl, mono (C1-C6) substituted alkoxy phenyl (C1-C3) alkyl, C1-C6 alkyloxy (C2-C4) alkyl, C3-C7 cycloalkyl, mono (C1-C4) alkyl substituted C3-C7 cycloalkyl, C1-C6 haloalkyl, allyl, benzoyl, monosubstituted benzoyl, naphthoyl or monosubstituted naphthoyl, said group of benzoyl and naphthoyl substituents being C1-C6 alkyl or C1-C6 alkoxy; or R5 is -CH (R6) Q, wherein R6 is hydrogen or C1-C3 alkyl and Q is -CN, -CF3, or -C00R7, and R7 is hydrogen or C1-C3 alkyl; or R5 is the group -C (O) V wherein V is hydrogen, C1-C6 alkoxy, phenoxy, phenoxy mono- or di- (C1-C6) substituted alkyl, phenoxy mono- or di- (C1-C6) ) substituted alkoxy, an unsubstituted, mono- or di-substituted aryl group, amine, mono (C1-C6) alkylamine, di (C1-C6) alkylamine, phenylamine, mono- or di (C1-C6) alkylamine substituted mono- or di- (C1-C6) alkoxy substituted phenylamine, said substituent aryl groups being C1-C6 alkyl or C1-C6 alkoxy; (V) a group, -CH (Q ') 2, wherein Q' is -CN or -C00R8, where R8 is hydrogen, C1-C6 alkyl, phenyl (C1-C3) alkyl, mono (C1 C1-6 alkyl substituted phenyl (C1-C3) alkyl, mono (C1-C6) substituted alkoxy phenyl (C1-C3) alkyl, or an unsubstituted mono- or di-substituted aryl group each of said substituents of aryl group being C1-C6 alkyl or C1-C6 alkoxy; (Vi) a group, -CH (R9) G, wherein R9 is hydrogen, C1-C6 alkyl or an unsubstituted, mono- or disubstituted aryl group, and G is hydroxy, C1-C6 alkoxy , aryloxy, amine, mono (C1-C6) alkylamine, di (C1-C6) alkylamine, phenylamine, substituted mono- or di- (C1-C6) alkylamine, or mono- or di (C1-C6) alkoxy phenylamine substituted, -C00R8, -CORIO or -CH20R11, wherein RIO is hydrogen, C1-C6 alkyl, an unsubstituted, mono- or disubstituted aryl group, amine, mono (C1-C6) alkylamine, di (C1- C6) alkylamine, phenylamine, phenyl mono- or di- (C1-C6) substituted alkyl, phenyl mono- or di- (C1-C6) substituted alkoxy, diphenylamine, diphenylamine mono- or di (C1-C6) alkyl substituted, diphenylamine mono- or di (C1-C6) substituted alkoxy, morpholine, or piperidine, wherein R11 is hydrogen, -C (O) R8, C1-C6 alkyl, C1-C3 (C1-C6) alkyl, phenyl (C1-6) C3) alkyl, mono (C1-C6) substituted alkoxy phenyl (C1-C3) alkyl, or an unsubstituted aryl group o, mono- or disubstituted, each of said substituent aryl groups being C1-C6 alkyl or C1-C6 alkoxy; and (vii) a group, T, represented by the formula: [0025] -Z [(OC2H4) x (OC3H6) y (OC4H8) z] Z '[0026] or [0027] - [(OC2H4) x (OC 3 H 6) y (OC 4 H 8) z] Z 'wherein' -Z is -C (O) - or -CH 2 -, Z 'is C 1 -C 3 alkoxy or a polymerizable group for example any functional group capable of to participate in a polymerization reaction. Polymer formation methods in which the polymerizable compounds of the present invention may participate include radical polymerization, and such other polymerization processes as described in Ullmann's Encyclopedia of Industrial Chemistry, "Polymerization Processes", Vol. 21A, pp 305 to 428. The polymerizable groups may be selected from the group consisting of hydroxy, (methyl) acryloxy, vinyl, isocyanate and epoxy, for example oxiranylamethyl. When there are 2 or more polymerizable groups in naphthopyran, they may be the same or different, x, y and z are each a number between 0 and 50, and the sum of x, y and z is between 2 and 50; or (viii) R 1 and R 2 may together form a substituted or unsubstituted spiro carbocyclic ring containing from 3 to 6 carbon atoms or a substituted or unsubstituted spiroheterocyclic group containing 1 or 2 oxygen atoms and 3 at 6 carbon atoms including the spirocarbon atom, said spiro-carbocyclic ring and the spiroheterocyclic group being ringed with 0, 1 or 2 benzene rings, said substituents being hydrogen or C1-C6 alkyl as long as said spiro-carbocyclic ring is not fluorene-9-ylidene. In one contemplated embodiment, R1 and R2 are each selected from the group consisting of: (i) hydrogen, hydroxy, C1-C6 alkyl, C1-C6 haloalkyl, disubstituted amine, C3- C7 cycloalkyl, benzyl, monosubstituted benzyl and the group, -C (O) W, wherein W is C1-C6 alkoxy, di (C1-C6) alkylamine, morpholine or piperidine, said amine substituents being C1-C6 alkyl, said benzyl substituents being C1-C6 alkyl or C1-C6 alkoxy; (Ii) mono- and di- and tri-substituted members selected from the group consisting of phenyl, naphthyl and dibenzofuranyl, said group of substituents being selected from the group consisting of C1-C6 alkyl, C1- C 6 alkoxy, and disubstituted amine, said amine substituents being C 1 -C 6 alkyl; Mon substituted phenyl having a substituent at the position for which it is a -0- (CH2) t- linking group, where t is the integer 3, 4 or 5 attached to an aryl group which is a member of another photochromic naphthopyran (iv) a group, -OR5, wherein R5 is C1-C6 alkyl, C1-C6 acyl, C1-C6 (C2-C4) alkyloxy, benzoyl or mono-substituted benzoyl, said benzoyl substituents being C1-C6 alkyl or C1-C6 alkoxy; or R5 is the group -CH (R6) Q, wherein R6 is hydrogen and Q is -C00R7, and R7 is C1-C3 alkyl; or R5 is the group -C (O) V wherein V is C1-C6 alkoxy or di (C1-C6) alkyl amine; (V) a group, -CH (Q ') 2, wherein Q' is -C00R8, wherein R8 is C1-C6 alkyl, or phenyl (C1-C3) alkyl; (Vi) a group, -CH (R9) G, wherein R9 is C1-C6 alkyl, and G is C1-C6 alkoxy, -C00R8 -COR10, or -CH20R11, where R10 is C1-C6 alkyl di (C1-C6) alkylamine, morpholine or piperidine; wherein R11 is C1-C6 alkyl or C1-C3 (C1-C6) alkoxy alkyl, and a group, T, represented by the formula: [0038] - [(OC2H4) x (OC3H6) y ( OC4H8) z] Z 'wherein Z' is C1 -C3 alkoxy or a polymerizable group, x, y and z are each a number between 0 and 50, and the sum of x, y and z is between 2 and 50; or (viii) R1 and R2 may together form a substituted or unsubstituted oxo group or spiroheterocyclic group containing 1 or 2 oxygen atoms and 3 to 6 carbon atoms including the spiro carbon atom, the said heterocyclic spiro ring being ringed with 1 or 2 benzene rings, said substituent being C1-C6 alkyl. In another contemplated embodiment, R1 and R2 are each selected from the group consisting of: (i) hydrogen, hydroxy, C1-C3 alkyl and the group, -C (0) W, in which W is C1 -C6 alkoxy; (Ü) unsubstituted and monosubstituted phenyl, said phenyl substituents being selected from the group consisting of C1-C6 alkoxy, and disubstituted amine, said amine substituents being C1-C3 alkyl; (Iü) monosubstituted phenyl having a substituent at the position for which it is a linking group, -0- (CH2) t-, where t is an integer 3, connected to an aryl group, which is a member of another photochromic naphthalopyran; (Iv) a group, -OR5, wherein R5 is C1-C6 alkyl, C1-C6 (C2-C4) alkyloxy, the -CH (R6) Q group, where R6 is hydrogen or C1-C3 alkyl and Q is -C00R7, and R7 is C1-C3 alkyl or R5 is the group, -C (O) V, wherein V is C1-C6 alkoxy; (V) a group, -CH (Q ') 2, wherein Q' is -C00R8, wherein R8 is C1-C6 alkyl; (Vi) a group, -CH (R9) G, wherein R9 is C1-C6 alkyl, and G is C1-C6 alkoxy, -C00R8, -COR10 or -CH20R11 wherein R10 and R11 are each C1 -C6 alkyl; and (vii) a group, T, represented by the formula: where Z 'is C1-C3 alkoxy or a polymerizable group x, y and are each a number between 0 and 50, and the sum of x, y and z is between 2 and 50; or (viii) R1 and R2 may together form a substituted or unsubstituted spiroheterocyclic group containing 1 oxygen atom and 6 carbon atoms including the spirocarbon atom, said spiroheterocyclic ring being ringed with 2 benzene rings, said substituents being C1 -C3 alkyl. R3 may be selected from the substituent group known in the art for use in photochromic compounds. Each R3 in formula I may be independently selected from the group consisting of hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C3-C7 cycloalkyl, phenyl, benzyl, di (C1-C6) alkylamine, dicyclohexylamine, diphenylamine, piperidyl, morpholinyl, pyridyl, halogen, a group, T, and the group -C (0) W en is the integer 0, 1, or 2; or when n is at least 2, and the substituents of R3 are adjacent, the pair of substituents form a substituted or unsubstituted fused carbocyclic or heterocyclic ring selected from the group consisting of benzo, pyridine, pyrazine, pyrimidine, furan, dihydrofuran 1,3-dioxolo, 1,4-dioxolo, 1,3-dioxino, 1,4-dioxino, thiophene, benzofuro, benzothiene, indole, and indene, the substituents of said fused carbocyclic or heterocyclic ring being selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy, amine, mono- and disubstituted amine, said amine substituents being selected from the group consisting of C1-C6 alkyl, phenyl, benzyl and naphthyl ; said first ring R3 being fused to side o, p or q and said second ring R3 being fused to side g, h, or i of naphthopyran. In a contemplated embodiment, R3 is selected from the group consisting of hydrogen, C1-C6 alkyl, C1-C6 alkoxy, di (C1-C6) alkylamine, piperidyl, morpholinyl, pyrrolidyl, halogen, a group, T , or the group, -C (0) W en is the integer 0, 1, or 2; or when n is 2, and substituents R 3 are adjacent, a pair of substituents form a substituted or unsubstituted fused carbocyclic or heterocyclic ring selected from the group consisting of benzo, dihydrofuran and benzofuro, the substituents on said carbocyclic or heterocyclic ring fused being selected from the group consisting of C1-C6 alkyl, C1-C6 alkoxy, and disubstituted amine, said amine substituents being C1-C6 alkyl; said ring R 3 being fused to the o, p or q sides of naphthalopyran. In another contemplated embodiment, each R 3 is selected from the group consisting of C1-C6 alkyl hydrogen, C1-C6 alkoxy, morpholinyl, a group, T, and the group -C (0) W, and when m is 2 and the substituents of R3 are adjacent, the pair of substituents form a substituted or unsubstituted fused carbocyclic or heterocyclic ring selected from the group consisting of benzo and benzofuro, the substituents of said fused carbocyclic or heterocyclic ring being C1-4. C6 alkoxy; said ring of R3 being fused to the β side of naphthalopyran. In the formula I, R1, R2 and each R3 are the same as described hereinbefore in the formula I '.

In the definitions of R1, R2, R3, B and B ', similar substituents have similar meanings. [0056] B and B 'in graphic formula I may each be selected from the group of substituents known in the art for use in photochromic compounds. Specifically, B and B 'may each be selected from the group consisting of: [0057] (i) monosubstituted phenyl [0058] (ü) an unsubstituted aryl group, mono-, di-, and tri-substituted; (Iü) Unsubstituted, mono- or disubstituted 9-julolidinyl heteroaromatic group selected from the group consisting of pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothieno-2 -yl, benzothieno-3-yl, dibenzofuranyl, dibenzothienyl, carbazoyl, benzopyridyl, indolinyl and fluorenyl, each of said aryl and heteroaromatic substituents in (ii) and (iii) being selected from the group consisting of hydroxy, aryl for example phenyl and naphthyl, mono (C1-C6) alkoxyaryl, di (C1-C6) alkoxyaryl, mono (C1-C6) alkylaryl, di (C1-C6) alkylaryl, haloaryl, C3-C7 cycloalkylaryl, C3-C7 cycloalkyl, C3-C7 cycloalkyloxy, C3-C7 cycloalkyloxy (C1-C6) alkyl, C3-C7 cycloalkyloxy (C1-C6) alkoxy, aryl (C1-C6) alkyl, aryl (C1-C6) alkoxy, aryloxy, aryloxy (C6) alkyl, (C1-C6) alkoxy, mono- and di- (C1-C6) alkylaryl (C1-C6) alkyl, mono- and di (C1-C6) alkyl (C1-C6) alkyloxy, mono - and di (C1-C6) alkylaryl (C1-C6) alkoxy, m ono- and di- (C1-C6) alkoxy (C1-C6) alkoxy, amine, mono (C1-C6) alkylamine, di (C1-C6) alkylamine, diarylamine, (C1-C6 alkyl) amine, piperazine, N - (C1-C6) alkylapiperazine, N-arylapiperazine, aziridine, indoline, piperidine, morpholine, thiomorpholine, tetrahydroquinoline, tetrahydroisoquinoline, pyrrolidyl, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, mono (C1-C6) ) (C1 -C4) alkoxy alkyl, acryloxy, methacryloxy and halogen; (Iv) an unsubstituted or monosubstituted member selected from the group consisting of pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrolinyl, phenothiazinyl, phenoxazinyl, phenazinyl and acridinyl, each of these substituents being selected from the group. group consisting of C1-C6 alkyl, C1-C6 alkoxy, phenyl, and halogen; (V) monosubstituted phenyl having a substituent at the position for which it is a - (CH2) t- or -0- (CH2) t- linking group, where t is the integer 1, 2, 3, 4, 5 or 6, connected to an aryl group which is a member of another photochromic naphthalopyran (vi 5) a group represented by one of the following graphic formulas 11A or IIB: wherein A is methylene or oxygen ED is oxygen or substituted nitrogen, provided that when D is substituted nitrogen, A is methylene, said nitrogen substituent being selected from the group consisting of hydrogen, C1-C6 alkyl, and C2-C6 acyl; 2 is C 1 -C 6 alkyl, C 1 -C 6 alkoxy, hydroxy, or halogen; R 13 and R 14 are each hydrogen or C 1 -C 6 alkyl, and Q is the integer 0, 1, or 2; C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 (C1-C4) alkoxy alkyl, C3-C6 cycloalkyl, mono (C1-C6) alkoxy (C3-C6) cycloalkyl, mono (C1-C6) alkyl-C3-C6 ) -cycloalkyl, (C3 -C6) cyclohalo quyl, and C 4 -C 12 bicycloalkyl; and (vii) a group represented by the following formula IIC: wherein L is hydrogen or C 1 -C 4 alkyl and M is selected from unsubstituted members , mono-, and disubstituted from the group consisting of naphthyl, phenyl, furanyl, and phenylen, each of said substituent groups being C1-C4 alkyl, C1-C4 alkoxy, or halogen. Alternatively, B and B 'may together form fluorene-9-ylidene, mono-, or disubstituted fluorene-9-ylidene or form a member selected from the group consisting of C3-C12 spiro-monocyclic rings saturated hydrocarbons, for example, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylene, cyclooctylene, cyclononylidene, cyclodecylidene cycloundecylidene, cyclododecylidene; saturated C 7 -C 12 spiro-bicyclic hydrocarbon rings, eg bicyclo [2.2.1] heptylidene, eg norbornylidene, 1,7,7-trimethyl bicyclo [2.2.1] heptylidene, eg bornylidene, bicyclo [3.2 .1] octylidene, bicyclo [3.3.1] nonan-9-ylidene, bicyclo [4.3.2] undecane, and C 7 -C 12 spiro-tricyclic saturated hydrocarbon rings, for example tricyclo [2.2.1.02,6] heptylidene , tricyclo [3.3.1.13,7] decylidene, for example adamantylidene, and tricyclo [5.3.1.12,6] dodecylidene, each of fluorene-9-ylidene substituents being selected from the group consisting of C1-C4 alkyl C1 -C4 alkoxy and halogen. In one contemplated embodiment, B and B 'are each selected from the group consisting of: (i) phenyl, monosubstituted phenyl, and disubstituted phenyl, preferably meta and / or para substituted; (ii) the unsubstituted, mono- and disubstituted heterocyclic aromatic groups of furanyl, benzofuran-2-yl, thienyl, benzothien-2-yl and dibenzofuranyl, each of said phenyl and heterocyclic aromatic substituents being selected from from the group consisting of hydroxy, amine, mono (C1-C3) alkylamine, di (C1-C3) alkylamine, piperidine, morpholine, pyrryl, C1-C3 alkyl, C1-C3 chloroalkyl, C1-C3 fluoroalkyl, C1-C3 alkoxy mono (C1-C3) alkoxy (C1-C3) alkyl, fluoro and chloro; (iii) the groups represented by the graphic formulas IIA and IIB, wherein A is methylene and D is oxygen, R12 is C1-C3 alkyl or C1-C3 alkoxy, R13 and R14 are each hydrogen or C1-C4 alkyl; and q is the integer 0 or 1; (iv) C1 -C4 alkyl; and (v) the group represented by the formula IIC wherein L is hydrogen or methyl and M is phenyl or monosubstituted phenyl, said phenyl substituent being selected from the group consisting of C1-C3 alkyl, C1-C3 alkoxy and fluoro; or (vi) B and B 'together form fluorene-9-ylidene, monosubstituted fluorene-9-ylidene or a member selected from the group consisting of C3-C8 spiro-monocyclic saturated hydrocarbon rings, C1-4 rings. C10 spiro-bicyclic saturated hydrocarbons, and rings of C7-C10 spiro-tricyclic saturated hydrocarbons, said fluorene-9-ylidene substituent being selected from the group consisting of C1-C3 alkyl, C1-C3 alkoxy, fluoro and chloro . In another contemplated embodiment, B and B 'are each selected from the group consisting of (i) phenyl, mono- and disubstituted phenyl, (ii) unsubstituted heterocyclic aromatic groups, mono- and disubstituted furanyl, benzofuran-2-yl, thienyl, benzottieno-2-yl and dibenzofuranyl, each of said phenyl and aromatic heterocyclic substituents being selected from the group consisting of hydroxy, C1-C3 alkyl, C1- C3 alkoxy, piperidine and morpholine; and (iii) the group represented by the formula IIA, wherein A is methylene and D is oxygen, R12 is C1-C3 alkyl or C1-C3 alkoxy, R13 and R14 are each hydrogen or C1-C3 alkyl, eq is integer 0 or 1; or (iv) B and B 'together form fluorene-9-ylidene, adamantylene, bornylidene, norbornylidene, or bicyclo [3.3.1] nonane-9-ylidene. The compounds represented by graphic formula I having some of the R1-R3, B and B 'described hereinbefore, may be prepared by the following reactions A to G.

Methods for the preparation of compounds in which R1, R2, B and / or B 'is the polyalkoxy group T are described in U.S. Patent No. 5,961,892. Methods for the preparation of compounds wherein R1, R2, B and / or B 'is the polyalkoxylated polymerizable T group are described in U.S. Patent No. 6,113,814. With reference to the following reactions, the compounds represented by the formula V or VA are either purchased or prepared by Friedel-Crafts methods shown in Reaction A using a substituted or unsubstituted benzoyl chloride of the formula IV with a compound of substituted or unsubstituted benzene of commercially available formula III. See Friedel-Crafts and Related Reactions, George A. Olah, Interscience Publishers, 1964, Vol. 3, Chapter XXXI (Aromatic Ketone Synthesis), and "Regioselective Friedel-Crafts Acylation of 1,2,3,4- Tetrahydroquinoline and Related Nitrogen Heterocycles: Effect on NH Protective Groups and Ring Size "by Ishihara, Yugi et al, J.

Chem. Soc., Perkin Trans. 1, pages 3401 to 3406, 1992. In Reaction A, the compounds represented by graphic formulas III and IV are dissolved in a solvent, such as carbon disulfide or methylene chloride, and reacted in the presence of a Lewis acid. , such as aluminum chloride or tin tetrachloride, to form the corresponding substituted benzophenone represented by the formula V (VA in Reaction B). R and R 'represent possible substituents as described hereinbefore with respect to B and B' of graphic formula I.

REACTION A In Reaction B, the substituted or unsubstituted ketone represented by the formula VA, where Be B 'may represent groups other than those of substituted or unsubstituted phenyl, as shown in the formula V, is reacted. with sodium acetylide in a suitable solvent, such as anhydrous tetrahydrofuran (THF), to form the corresponding propargyl alcohol represented by the formula VI. Propargyl alcohols having groups B and B 'other than those of substituted phenyl and not Substituted may be prepared from commercially available ketones or ketones prepared via a reaction of an acyl halide with a substituted or unsubstituted benzene, a naphthalene or heteroaromatic compound, for example 9-julolidinyl. Propargyl alcohols having a group B or B 'represented by the formula IIC may be prepared by the methods described in U.S. Patent No. 5,274,132, column 2, lines 40 to 68.

REACTION B In Reaction C, a substituted or unsubstituted Î ± -methoxy naphthalene represented by the formula VII is reacted with a benzoyl (IV) chloride in the presence of an anhydrous aluminum chloride to form a naphtophenone represented by the formula VIII . Compound VIII is reacted with an organometallic compound containing R1 to give a carbinol compound represented by the formula IX. Compound IX is heated with phosphoric acid to afford the acetone represented by formula X. Compound X is flavored by reaction with a base such as KOH in a water / ethanol mixture to produce the indene-fused naphthol of formula XI.

In Reaction D, an orbromo acetophenone represented by the formula XII is reacted with ethyl, (X-benzoylacetate represented by the formula XIII in the presence of sodium hydride and cuprous bromide to form a naphthol represented by Naphthol XIV is then hydrolyzed with an aqueous base followed by cyclization to a strong acid such as phosphoric acid to produce the indene-fused naphthol represented by the formula XV.

In Reaction E, the naphthol represented by the graphic formula XI is coupled with a propargy alcohol (VI) in the presence of a catalytic amount of an acid such as p-dodecylbenzene sulfonic acid to form an indenaphthopyran represented by the graphic formula. IA Compound IA is reacted with a strong base such as liter of butyl or KOH and followed by reaction with alkyl halide to produce indenaphtopyran represented by the formula IB.

REACTION E In reaction F, the naphthol represented by the graphic formula XV is coupled with a propargy alcohol to give the indenonaptopyran represented by the graphic formula XVI. Compound XVI is reacted with an organo metal compound to yield the indenaphtopyran of formula IC. The hydroxy group in compound IC is alkylated with alcohol to form an ether substituent on indenaphtopyran of formula ID. In Reaction G, the orthobromoacetophenone represented by the formula XII is reacted with diethyl malonate represented by the formula XVII in the presence of sodium hydride and cuprous bromide to form a dihydroxy naphthaene represented by the formula XVIII. Compound XVIII is coupled with a propargyl (VI) alcohol to produce the naphthopyran represented by the formula IXX. Compound IXX is methylated with methylene iodide in the presence of potassium carbonate to form · naphthopyran represented by the formula XX. The reaction of Grignard's aryl reagent represented by the graphic formula XXI with the compound XX produces the naphthopyran represented by the graphic formula XXII. Compound XXII is reacted with alkyl lithium to yield a carbinol derivative represented by the formula XXIII. Cyclization of compound XXIII with acid forms the desired indenaphtopyran represented by the formula IE. The compounds represented by graphic formula I may be used in those applications in which photochromic organic substances may be employed, such as optical lenses, for example ophthalmic vision correction lenses, contact lenses and flat lenses, face shields, diving masks, visors, camera lenses, windows, car windshields, aircraft and car transparencies, for example, sunroofs, side lights and taillights, plastic sheeting, textiles and coverings, coating compositions As used herein, coating compositions herein include polymeric coating compositions prepared from materials such as polyurethanes, epoxy resins and other resins used to produce synthetic polymers, paints, for example, a liquid or a paste pigments used for the decoration, protection and / or identification of a substance rat, and inks, for example, a pigmented liquid or paste used for writing and printing on substrates. Potential substrates for coating compositions containing the compounds of the present invention include paper, glass, ceramics, wood, masonry, textiles, metals and organic polymeric materials. Coating compositions may be used to produce optical coatings, mark verification on security documents, eg banknotes (cash), passports and driving licenses for which Authentication and verification of authenticity may be desired. The indenonaftopyranes represented by the formula I exhibit color changes from colorless to colors ranging from yellow / brown to blue / gray. Examples of indenaphtopyran compounds within the scope of the invention are as follows: (a) 3,3,9-triphenyl-3H-9H-indene [3 ', 2': 3,4] naphtho [ 1,2-b] pyran; (B) 3,3-di (4-methoxyphenyl) -9-phenyl-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b] pyran; (C) 3- (4-methoxyphenyl) -3,9-diphenyl-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b] pyran; (D) 3- (4-morpholinephenyl) -3,9-diphenyl-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b] pyran; (E) 3,3-di (4-methoxyphenyl) -9- (3-methoxyphenyl) -1H-methoxy-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2 -b] pyran; (F) 3- (4-Methoxyphenyl) -3-phenyl-9- (3-methoxyphenyl) -1H-methoxy-3H-9H-indene [3 ', 2': 3,4] naphtho [1, 2-b] pyran; (G) 3- (4-Methoxyphenyl) -3-phenyl-9-methyl-11-methoxy-9- (3-methoxyphenyl) -3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b] pyran; (H) 3,3-di (4-methoxyphenyl) -9-methylal-11-methoxy-9- (3-methoxyphenyl) -3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b] pyran; (I) 3,3-di (4-methoxyphenyl) -9-methyl-11-methoxy-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b] pyran ; (J) 3,3-di (4-methoxyphenyl) -9,9-dimethyl-11-methoxy-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b ] pyran; (K) 3- (4-Methoxyphenyl) -3-phenyl-9,9-dimethyl-11-methoxy-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2- b] pyran; (1) 3,3-di (4-methoxyphenyl) -9,9-dimethyl-7,11-dimethoxy-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2 -b] pyran; (M) 3- (4-Methoxyphenyl) -3-phenyl-9,9-dimethyl-7,11-dimethoxy-3H-9H-indene [3 ', 2': 3,4] naphtho [1, 2-b] pyran; (N) 3- (4-morpholinphenyl) -3-phenyl-9,9-dimethyl-7,11-dimethoxy-3H-9H-indene [3 ', 2': 3,4] naphtho [1, 2-b] pyran; (O) 3,3-di (4-methoxyphenyl) -9-methyl-11,13-dimethoxy-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b ] pyran; (P) 3- (4-Methoxyphenyl) -3-phenyl-9-methyl-11,13-dimethoxy-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2- b] pyran; (Q) 3- (4-Methoxyphenyl) -3-phenyl-9,9-dimethyl-3H-9H-benzo [4 ", 5"] indene [3 ', 2': 3,4] naphtho [ 1,2-b] pyran; and (r) 3,3-di (4-methoxyphenyl-9,9-dimethyl-11-fluoro-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b [0099] It is contemplated that the photochromic indenaphthyropyrams of the present invention may each be used alone or in combination with other indenaphthyropyranes of the present invention Alternatively, the photochromic indenonephropyranes of the present invention may be used in combination with one or more Other suitable complementary photochromic organic materials, for example photochromic organic compounds having at least a maximum activated absorption within the range of 400 and 700 nanometers, or substances containing the same Photochromic compounds may be incorporated, for example, dissolved or dispersed, in a host organic polymeric material used for the preparation of staining photochromic articles when activated to an appropriate shade. [00100] Complementary photochromic organic materials may include: ndenonaphthyranes, naphthopyran, benzopyran, phenanthropyran, spiro (benzindoline) naphthopyran, spiro (indoline) benzopyran, spiro (indoline) naphtopyrane, spiro (indoline) quinopyran, spiro (indoline) pyran, spiro (indoline), spiroxino (pyridine) spiro (benzindoline) pyridobenzoxazine, spiro (benzindoline) naphthoxazine, spiro (indoline) benzoxazine, organo-metalditizonates, for example mercury dizzonates, fulgidos, fulgimides and mixtures of such photochromic compounds. Such photochromic compounds are described in U.S. Pat. 5,645,767 and 6,153,126. The photochromic compounds of the present invention may be associated with a host organic polymeric material or other substrate in various ways. They may be incorporated, for example, dissolved and / or dispersed within the host material, polymerized with other components of the host material, and / or incorporated within a coating applied to a substrate, for example a polymeric coating applied to a surface of a host organic polymeric material. Each of the photochromic substances described herein may be used in amounts (or in a ratio) such that a host organic material or substrate in which photochromic compounds or mixtures of the compounds are associated exhibits a desired resulting color, for example, a substantially neutral color when activated with unfiltered sunlight, for example as close as possible to the neutral color given the colors of the activated photochromic compounds. Neutral gray and neutral brown are preferred. Further discussion of neutral colors and ways of describing colors can be found in U.S. Patent No. 5,645,767 column 12, line 66 through column 13, line 19. The amount of photochromic indenonaptopyrans to be applied to or incorporated into a Coating composition or host material is not critical as long as sufficient amount is used to produce a photochromic effect noticeable to the naked eye once activated. Generally such amount can be described as a photochromic amount. The particular amount used often depends on the desired color intensity upon irradiation over the article and the method used to incorporate or apply the photochromic compounds. Typically, the more photochromic compound is applied or incorporated, the more pronounced the color intensity is up to a certain limit. The relative amounts of the above mentioned photochromic compounds used will vary and will depend in part on the relative color intensities of the activated species of such compounds, the desired final color and the method of application to the host material or substrate. Generally, the amount of the total photochromic compound incorporated into or applied to the host photochromic optical material may range from 0.05 to 2.0, for example from 0.2 to 1.0 milligrams per square centimeter of the surface to which the photochromic compound is incorporated or applied. . The amount of photochromic material incorporated into a coating composition may range from 0.1 to 40 weight percent based on the weight of the liquid coating composition. The photochromic indenonaptopyranes of the present invention may be associated with the host material by various methods described by the art. See, for example, column 13, lines 40 to 58 of U.S. Patent No. 5,645,767. Aqueous or organic solutions or dispersions of the photochromic compound may be used to incorporate the photochromic compound into a host organic polymeric material or other materials such as textiles and coating compositions. Coating compositions may be applied to the substrate using a coating process as described in U.S. Pat. 3,971,872. 6,025,026 and 6,150,430. Application of the polymeric coating may be accomplished by any of the methods used in coating technology such as, for example, spray coating, spin coating, expansion coating, curtain coating, dip coating, casting or coating. by rollers and methods used in the preparation of overlays, such as the method described in U.S. Patent No. 4,873,029. The method of application selected also depends on the thickness of the cured coating. Coatings having a thickness ranging from 1 to 50 microns may be applied by conventional methods used in coating technology. Coatings with a thickness greater than 50 microns may require the methods typically used for overlays. The polymeric coating composition includes compositions that result in thermoplastic or thermocured coatings which are described in Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Volume 6, pages 669 to 760. The coating may comprise at least one polymer. selected from the group consisting of polyurethanes, melamine resins, polyvinyl alcohol, polyacrylates, polymethacrylates, polyamide resins and epoxy resins. Such polymer coating compositions are described in U.S. Patent No. 4,425,403. The host material will usually be transparent, but may be translucent or even opaque. The host material need only be susceptible to that portion of the electromagnetic spectrum which activates the photochromic substance, for example, that wavelength of ultraviolet light (UV) that produces the open or closed form of the substance and that portion of the visible spectrum that includes the maximum absorption wavelength of the substance in its UV-activated form, for example, the open form. Preferably, the host color should not be such that it masks the color of the activated form of photochromic compounds, for example, such that the color change is readily apparent to the observer. Compatible dyes may be applied to the host material as described in U.S. Patent No. 5,645,767 in column 13, Line 59 to column 14, line 3. More preferably, the organic host polymeric material is a transparent or optically clear solid material. for example materials suitable for optical applications such as flat, ophthalmic and contact lenses, windows, automotive transparencies, eg windshields, aircraft transparencies, plastic sheeting, polymeric films, etc. Examples of a host organic polymeric material which may be used with the photochromic compound described herein include: polymers, for example, homopolymers and copolymers, bis (allyl carbonate) monomers, diethylene glycol dimethacrylate monomers, diisopropenyl benzene, bisphenol A monomers ethoxylated dimethacrylate, ethylene glycol bismethacrylate monomers, poly (ethylene glycol) bismethacrylate monomers, ethoxylated bismethacrylate phenol monomers, alkoxylated acrylate polyhydric acrylate monomers of propylate trimethane monomers acrylate, such as those described in U.S. Patent No. 5,373,033, and vinylabenzene monomers, such as those described in U.S. Patent No. 5,475,074 and styrene; polymers, for example, mono- or polyfunctional homopolymers and copolymers, for example di- or multifunctional, acrylate and / or methacrylate monomers, poly (C1-C12 alkyl methacrylates) such as poly (methyl methacrylate), poly (oxyalkylene) ) dimethacrylate, poly (alkoxylated phenol methacrylates), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly (vinyl acetate), poly (vinyl alcohol), poly (vinyl chloride), poly (vinylidene) chloride), polyurethanes, polythiurethanes, thermoplastic polycarbonate, polyesters, poly (ethylene terephthalate), polystyrene, poly (alpha methylstyrene), copoly (styrene-methyl methacrylate), copoly (styrene-acrylonitrile), polyvinyl butyral and polymers, for example, homopolymers and copolymers of diallylidene pentaerythritol, particularly copolymers with polyol (allyl carbonate) monomers, for example diethylene glycol bis (allyl carbonate), and acrylate monomer, for example ethyl acrylate, butyl acrylate.

Additional examples of a host organic polymeric material are disclosed in U.S. Patent No. 5,753,146, column 8, line 62 to column 10, line 34. Transparent copolymers and transparent polymer blends are also suitable as host materials. Preferably, the host material or substrate for the polymeric photochromic coating composition is an optically clear organic polymerized material prepared from a thermoplastic polycarbonate resin, such as carbonate-bonded resin derived from bisphenol A and phosgene, which is sold under the trademark LEXAN; a polyester, such as material sold under the trademark MYLAR; a poly (methyl methacrylate), such as material sold under the trademark PLEXIGLAS; polymerized articles of a polyol (allyl carbonate) monomer, especially diethylene glycol bis (allyl carbonate), which monomer is sold under the trademark CR-39, and polymerized articles of a polyol (allyl carbonate) copolymers, for example, diethylene glycol bis (allyl carbonate), with other monomeric copolymerizable materials such as vinyl acetate copolymers, for example, copolymers of from 80-90 percent of diethylene glycol bis (allyl carbonate) and 10-20 percent of vinyl, particularly 80-85 percent bis (allyl carbonate) and 15-20 percent vinyl acetate, and copolymers with a polyurethane having a terminal diacrylate functionality as described in U.S. Pat. 4,360,653 and 4,994,208; and aliphatic urethane copolymers, the terminal portion of which contains functional allyl or acrylyl groups, as described in U.S. Patent No. 5,200,483; poly (vinyl acetate), polyvinyl butyral, polyurethane, polythiurethanes, group member polymers consisting of diethylene glycol dimethacrylate monomers, benzene diisopropenyl monomers, bisphenol A ethoxylated dimethacrylate, ethylene glycol bismethacrylate monomers (polyethylene glycol monomers) ) bismethacrylate, ethoxylated bismethacrylate phenol monomers and ethoxylated trimethylol propane triacrylate monomers; cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, polystyrene and styrene copolymers with methyl methacrylate, vinyl acetate and acrylonitrile. More particularly contemplated is the use of photochromic indenonephtopyranes of the present invention with organic optical resin monomers used to produce optically clear coatings and polymerised articles, for example, materials suitable for optical applications, such as for example flat and ophthalmic lenses, windows. , and transparencies for cars.

Such optically clear polymerized articles may have a refractive index which may range from 1.48 to 1.75, for example from 1.495 to 1.66. Specifically contemplated are polymerized optical resin articles sold by PPG Industries, Inc. under the designation, for example, CR-307, CR-407 and CR-607 and polymerised articles prepared for use with soft contact lenses or hard. The methods for producing both types of contact lenses are disclosed in U.S. Patent No. 5,166,345, column 11, line 52, column 12, line 52. Additional polymerized articles contemplated for use with the photochromic naphthoopyran of the present invention. The invention is the polymerized articles used to form soft contact lenses with a high moisture content described in U.S. Patent No. 5,965,630 and extensive use contact lenses described in U.S. Patent No. 5,965,631. The present invention is more particularly described in the following examples, which are intended to be illustrative only, since numerous modifications and variations thereof will be apparent to those skilled in the art. EXAMPLE 1 STEP 1 1-methoxynaphthalene (100 grams), 108 grams of benzoyl chloride 600 milliliters (mL) of methylene chloride were mixed in a dry flask with the rounded bottom and stirred at room temperature. 3-5 ° C. Anhydrous aluminum chloride (100 grams) was slowly added to the reaction mixture and stirred for 2 hours. The reaction mixture was poured into a 2 liter 10% hydrochloric acid / ice mixture and stirred for half an hour. The organic layer was separated, washed with water and then 5 weight percent of an aqueous NaOH solution and again washed with water. The organic layer was dried over magnesium sulfate and filtered. The filtered material was concentrated and crystallized from hexane to give 160 grams of a solid product. Nuclear Magnetic Resonance (NMR) analysis showed that the product had a structure consistent with phenyl 1- (4-methoxynaphthyl) methanone. [00119] STEP 2 [00120] Phenyl 1- (4-methoxynaphthyl) methanone (3.5 grams, 13.3 millimoles) was dissolved in 60 mL anhydrous tetrahydrofuran under the nitrogen atmosphere in a reaction flask, and the reaction mixture was cooled to -5 ° C. Excess lithium phenyl (1.8 M solution, 14.3 mL) was added dropwise, stirred, and the reaction mixture was stirred overnight. The reaction mixture was quenched with water and acidified to pH 7 with 2 Normal (N) aqueous hydrochloric acid (HCl). The organic phase was separated, the solvents removed to quantitatively yield a yellow solid. Proton NMR and Mass Spectroscopy analysis showed that the product had a structure consistent with diphenyl- (1- (4-methoxy) naphthyl) methanol. STEP 3 Diphenyl- (1- (4-methoxy) naphthyl) methanol (2.39 grams, 7.03 millimole) was added, stirred, in a reaction flask containing pre-boiled o-phosphoric acid (50 mL). . The reaction mixture was heated to 100 ° C for a period of 50 minutes. The reaction mixture was poured over ice. The resulting organic precipitate was filtered off and washed with water. The aqueous phase was separated and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure.

The organic solids were combined to produce a yellowish solid which was then taken to the next step without further purification. Mass, Proton and Carbon-13 NMR Spectroscopy analysis showed that the product had a structure consistent with 7-phenyl-1,1b-dihydrobenzyl (a) fluorene-2-one. STEP 4 The yellow solid from Step 3 was added in a reaction flask containing toluene (100 mL). A solution of potassium hydroxide (1.75 grams) in 95% ethanol (50 mL) was added, and the reaction mixture was boiled for one hour. The organic solvents were removed under reduced pressure, ethyl acetate was added, and the mixture was washed with 2 N aqueous HCl to quench the residual base. The organic phase was separated and dried over anhydrous sodium sulfate, the solvent was removed under reduced pressure, and the residual oil was crystallized from hezanes to yield 1.85 grams of a brown powder. NMR analysis showed that the product had a structure consistent with 7-phenyl-benzo (a) fluorene-2-ol. STEP 5 7-Phenyl-benzo (a) fluorene-2-ol from Step 4 (0.4 grams) was added to a reaction flask containing 40 mL of chloroform. A catalytic amount of p-dodecylbenzene sulfonic acid (approximately 20 milligrams) was added, followed by 1,1-diphenyl-2-propyn-1-ol (0.21 grams) and the reaction mixture was stirred at room temperature for 24 hours. The solvent was removed under reduced pressure. The reaction mixture was separated by column chromatography using a 1: 2 mixture of dichloromethane: hexanes as eluent. The upper fraction was collected. The solvent was removed by evaporation and the residue was triturated with methanol to yield 0.21 grams of a light pink solid. Proton and Carbon-13 NMR and MS analysis showed that the product had a structure consistent with 3,3,9-triphenyl-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2- b] pyran. Example 2 The procedure of Example 1 was followed except that in Step 5, 1,1-bis (4-methoxyphenyl) -2-propin-1-ol was used in place of 1,1-diphenyl -2-propyn-1-ol to yield the desired product. NMR analysis showed that the product had a structure consistent with 3,3-di (4-methoxyphenyl) -9-phenyl-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2- b] pyran. Example 3 The procedure of Example 1 was followed except that in Step 5, 1-phenyl, 1- (4-methoxyphenyl) -2-propyn-1-ol was used in place of 1.1. diphenyl-2-propyn-1-ol and a 1: 9 mixture of ethyl acetate / hexanes was used as an eluent to yield the desired product. NMR analysis showed that the product had a structure consistent with 3- (4-methoxyphenyl) -3,9-diphenyl-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b ] pirane. Example 4 The procedure of Example 1 was followed except that in Step 5, 1-phenyl, 1- (4-morpholinphenyl) -2-propin-1-ol was used in place of 1.1. diphenyl-2-propyn-1-ol and a 1: 9 mixture of ethyl acetate / hexanes was used as an eluent to yield the desired product. NMR analysis showed that the product had a structure consistent with 3- (4-morpholinephenyl) -3.9-diphenyl-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b ] pirane. Example 5 The procedure of Example 1 was followed except that in Step 1, 3-methoxybenzoyl chloride was used in place of benzoyl chloride and in Step 2, 3-methoxyphenyl magnesium bromide was used. in place of lithium phenyl and in Step 5, 1,1-bis (4-methoxyphenyl) -2-propin-1-ol was used in place of 1,1-diphenyl-2-propin-1-ol and a mixture of 5: 4: 1 hexanes / dichloromethane / ethyl acetate was used as an eluent to produce the desired product. NMR analysis showed that the product had a structure consistent with 3,3-di (4-methoxyphenyl) -9- (3-methoxyphenyl) -1H-methoxy-3H-9H-indene [3 ', 2': 3, 4] naphtho [1,2-b] pyran. Example 6 The procedure of Example 5 was followed except that in Step 5, 1-phenyl, 1- (4-methoxyphenyl) -2-propyn-1-ol was used in place of 1.1. diphenyl-2-propyn-1-ol and a 5: 4: 1 mixture of hexanes / dichloromethane / ethyl acetate was used as an eluent to yield the desired product. NMR analysis showed that the product had a structure consistent with 3- (4-methoxyphenyl) -3-phenyl-9- (3-methoxyphenyl) -1H-methoxy-3H-9H-indene [3 ', 2': 3 , 4] naphtho [1,2-b] pyran. Example 7 The product of Example 6, 3- (4-methoxyphenyl) -3-phenyl-9- (3-methoxyphenyl) -1H-methoxy-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b] pyran (0.53 gram) was added in a reaction flask containing 20 mL anhydrous tetrahydrofuran. The reaction mixture was cooled to -78 ° C. N-Butyllithium (2.5 M in hexanes, 1.6 mL) was added by stirring with stirring under a nitrogen atmosphere. An immediate color change from light brown to dark brown was observed. The reaction mixture was stirred for 30 minutes, during which time methyl iodide (0.8 mL, 12.8 mmol) was added by stirring with stirring. The reaction mixture was stirred for 24 hours at room temperature. The solvents were removed under reduced pressure. The residue was treated with 20 mL of water. The organic solids were combined and separated by column chromatography using a 15: 4: 1 mixture of hexanes / dichloromethane / ethyl acetate as an eluent to yield 0.4 grams of a yellow solid product. Proton and carbon-13 MNR and MS analysis showed that the product had a structure consistent with 3- (4-methoxyphenyl) -3-phenyl-9-methyl-11-methoxy-9- (3-methoxyphenyl) -3H -9H-indene [3 ', 2': 3,4] naphtho [1,2- b] pyran. Example 8 The procedure of Example 7 was followed except that 3,3-di (4-methoxyphenyl) -9- (3-methoxyphenyl) -11-methoxy-3H-9H-indene [3 ' , 2 ': 3,4] naphtho [1,2-b] pyran was used in place of 3- (4-methoxyphenyl) -3-phenyl-9- (3-methoxyphenyl) -3H-9H-indene [3' 2 ': 3,4] naphtho [1,2-b] pyran to yield the desired product. Proton and Carbon-13 NMR and MS analysis showed that the product had a structure consistent with 3,3-di (4-methoxyphenyl) -9-methyl-11-methoxy-9- (3-methoxyphenyl) -3H- 9H-indene [3 ', 2': 3,4] naphtho [1,2-b] pyran. Example 9 The procedure of Example 1 was followed except that in Step 1, benzoyl 3-methoxychloride was used in place of benzoyl chloride and in Step 2, methyl magnesium chloride was used in place. of lithium phenyl and in Step 5, 1,1-bis (4-methoxyphenyl) -2-propin-1-ol was used in place of 1,1-diphenyl-2-propin-1-ol to yield the desired product. . NMR analysis showed that the product had a structure consistent with 3,3-di (4-methoxyphenyl) -9-methyl-11-methoxy-3H-9H-indene [3 ', 2': 3,4] naphtho [ 1,2-b] pyran. Example 10 The procedure of Example 7 was followed except that 3,3-di (4-methoxyphenyl) -9-methyl-11-methoxy-3H-9H-indene [3 ', 2': 3 , 4] naphtho [1,2-b] pyran was used in place of 3- (4-methoxyphenyl) -3-phenyl-9- (3-methoxyphenyl) -3H-9H-indene [3 ', 2': 3 , 4] naphtho [1,2-b] pyran to yield the desired product. Proton and Carbon-13 NMR and MS analysis showed that the product had a structure consistent with 3,3-di (4-methoxyphenyl) -9,9-dimethyl-11-methoxy-3H-9H-indene [3 ' , 2 ': 3,4] naphtho [1,2-b] pyran. Example 11 The procedure of Example 10 was followed except that in Step 5, 1- (4-methoxyphenyl) -1-phenyl-2-propyn-1-ol was used in place of 1.1. diphenyl-2-propyn-1-ol to yield the desired product. NMR analysis showed that the product had a structure consistent with 3- (4-methoxyphenyl) -3-phenyl-9,9-dimethyl-11-methoxy-3H-9H-indene [3 ', 2': 3.4 ] naphtho [1,2-b] pyran. Example 12 The procedure of Example 11 was followed except that in Step 1, 3-methoxybenzoyl chloride was used in place of benzoyl chloride and 1,6-dimethoxynaphthalene was used in place of 1-methoxynaphthene to produce the desired product. NMR analysis showed that the product had a structure consistent with 3,3-di (4-methoxyphenyl) -9,9-dimethyl-7,11-dimethoxy-3H-9H-indene [3 ', 2': 3, 4] naphtho [1,2-b] pyran. Example 13 The procedure of Example 12 was followed except that in Step 5, 1- (4-methoxyphenyl) -1-phenyl-2-propin-1-01 was used in place of 1.1. -di (4-methoxyphenyl) -2-propyn-1-ol to yield the desired product. NMR analysis showed that the product had a structure consistent with 3- (4-methoxyphenyl) -3-phenyl-9,9-dimethyl-7,11-dimethoxy-3H-9H-indene [3 ', 2': 3 , 4] naphtho [1,2-b] pyran. Example 14 The procedure of Example 12 was followed except that in Step 5, 1- (4-morpholinphenyl) -1-phenyl-2-propin-1-ol was used in place of 1.1. -di (4-methoxyphenyl) -2-propyn-1-ol to yield the desired product. NMR analysis showed that the product had a structure consistent with 3- (4-morpholinphenyl) -3-phenyl-9,9-dimethyl-7,11-dimethoxy-3H-9H-indene [3 ', 2': 3 , 4] naphtho [1,2-b] pyran. Example 15 The procedure of Example 9 was followed except that in Step 1, benzoyl 3,5-dimethoxychloride was used in place of benzoyl chloride to produce the desired product. NMR analysis showed that the product had a structure consistent with 3,3-di (4-methoxyphenyl) -9-methyl-11,13-dimethoxy-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b] pyran. Example 16 The procedure of Example 15 was followed except that in step 5, 1- (4-methoxyphenyl) -1-phenyl-2-propyn-1-ol was used in place of 1.1 -di (4-methoxyphenyl) -2-propyn-1-ol to yield the desired product. NMR analysis showed that the product had a structure consistent with 3- (4-methoxyphenyl) -3-phenyl-9-methyl-11,13-dimethoxy-3H-9H-indene [3 ', 2': 3.4 ] naphtho [1,2- b] pyran. Example 17 The procedure of Example 11 was followed except that in Step 1, 1-naphthoyl chloride was used in place of benzoyl 3-methoxychloride to produce the desired product. NMR analysis showed that the product had a structure consistent with 3- (4-methoxyphenyl) -3-phenyl-9,9-dimethyl-3H-9H-benzo [4 ", 5"] indene [3 ', 2' : 3,4] naphtho [1,2-b] pyran. Example 18 The procedure of Example 10 was followed except that in Step 1, benzoyl 3-fluorochloride was used in place of benzoyl 3-methoxychloride to produce the desired product. NMR analysis showed that the product had a structure consistent with 3,3-di (4-methoxyphenyl-9,9-dimethyl-11-fluoro-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b] pyran. [00161] COMPARATIVE EXAMPLE 1 The procedure of Comparative Example 1 of US Patent No. 5,645,767 was followed An NMR spectrum showed that the product had a structure consistent with 2, 2- di (4-methoxyphenyl), 5-methoxycarbonyl, 6-phenyl- [2 H] -naphtho [1,2-b] pyran. [00163] EXAMPLE 19 [00164] Part A [00165] The test was performed with the photochromic compound described in Examples 1 through 15, 17 and 18 and Comparative Example 1. As an amount of photochromic compound calculated to produce a 1.5 x 10-3 molar solution was added to a flask containing 50 grams of a mixture of 4-part bisphenol A ethoxylated dimethacrylate monomers (BPA 2EO DMA), 1 part poly (ethylene glycol) 600 dimethacrylate, and 0.033 weight percent 2,2'-azobis (2-methyl propionitrile) (AIBN).Photochromic compound was dissolved in the monomer mixture by stirring and gentle heating if necessary.

After a clear solution was obtained, it was poured into a flat sheet mold having the interior dimensions of 2.2 mm x 6 inches (15.24 cm) x 6 inches (15.24 cm). The mold was sealed and placed in a programmable horizontal air flow oven programmed to raise the temperature from 40 ° C to 95 ° C for a period of 5 hours, keep the temperature at 95 ° C for 3 hours, lower it. up to 60 ° C for a 2 hour interval and then keep it at 60 ° C for 16 hours. After the mold was opened, the polymer sheet was cut into test squares measuring 2 inches (5.1 centimeters) using a diamond blade saw. The photochromic property tests of Example 16 were performed as follows. A portion of the product was incorporated into a diethylene glycol dimethyl ether (diglyme) and irradiated with long wave ultraviolet light. The color of the sample has changed from light to brown. After irradiation was stopped, the color of the sample changed from brown to light.

[00167] Part B

[00168] Part A photochromic test squares were tested for photochromic response rates in an optical bank. Prior to optical bench testing, the photochromic test squares were exposed to 365 nanometers of ultraviolet light for approximately 15 minutes to activate the photochromic compound and then placed in a 76 ° C oven for approximately 15 minutes to bleach the photochromic compound. The test squares were then cooled to room temperature, exposed to ambient fluorescent lighting for at least 2 hours and then kept covered for at least 2 hours before testing in an optical bank maintained at 72 ° C. The bank was equipped with a lamp. 250-watt Xenon arc, a remote-controlled shutter, a copper sulfate bath acting as a heat sink, a Schott WG-320 nm cut-off filter which removes short-wavelength radiation; neutral density filter (s) and a sample holder into which the square to be tested was inserted. The optical bank's output power, for example, the dosage of light that the sample lens would be exposed to, was calibrated with a photochromic test square used as a reference standard. This resulted in an output power ranging from 0.15 to 0.20 milliwatts per square centimeter (mW / cm2). Output power measurement was performed using a GRASEBY Optronics Model S-371 Portable Photometer (Serial # 21536) with a UV-A detector (Serial # 22411) or comparable equipment. The UV-A detector was placed on the sample holder and the light output was measured. Output power adjustments were made by increasing or decreasing the lamp wattage or by adding or removing neutral density filters in the light path. A collimated beam of light monitoring from a tungsten lamp was passed through the square at a very small (approximately 30 °) normal angle to the square. After passing through the square, light from the tungsten lamp was directed to a detector through a monochromator assembly from Spectral Energu Corp. GM-200 at the predetermined maximum visible lambda of the photochromic compound being measured. The output signals from the detector were processed by a radiometer. The change in optical density (Δθϋ) was determined by inserting a test square in the bleach state into the sample holder, adjusting the transmittance scale to 100%, opening the shutter from the Xenon lamp to provide a ultraviolet radiation to change the test square from whiteness to an activated state (eg, darkened), thereby measuring transmittance in the activated state, and calculating the change in optical density according to the formula: AOD = log ( 100 /% Ta), where% Ta is the percent transmittance in the activated state and the logarithm is based on 10. A LABTECH NOTEBOOKpro software was used for all calculations. The optical properties of the photochromic compound in the test squares are reported in Table 1. 0 ΔΟϋ / Μίη, which represents the sensitivity of the photochromic compound response to UV light, was measured within the first five (5) seconds of exposure to UV, and then expressed on a per minute basis. Optical density saturation (Δθϋ @ Saturation) was performed under identical conditions as Δθϋ / Min, except that UV exposure was continued for 15 minutes. [00172] Lambda mx (Vis) is the wavelength in the visible spectrum at which the maximum absorption of the activated (colored) form of the photochromic compound in a test square occurs.

Max (Vis) lambda wavelengths reported in Table 1 were determined by testing the polymerized articles of Part A photochromic test squares on a Varian Cary 3 uv-visible spectrophotometer. Bleaching rate (1½) is the time interval in seconds for absorption of the activated form of photochromic compound in the test squares to read one half of the highest absorbance at room temperature (72 ° F, 22.2 ° C) after removal. of the activation light source. Each of the compounds of the Examples and Comparative Example exhibited dual peak absorbances in the visible spectrum (lambda max visible) in distinct color regions. For the highest visible max lambda (Band B), the corresponding optical density (AOD / Min and Δθϋ at saturation) and the bleaching rate (T 1/2) for the desired compounds of the Examples and Comparative Example are TABLE 1 Compound Bleaching Sensitivity Δθϋ @ Rate λ MAX (nm) Example Δθϋ / MIN Saturation T ½ sec Vis 1 (Band A) 416 1 (Band B) 0.12 0.30 147 516 2 (Band A) 440 2 ( Band B) 0.15 0.13 42 534 3 (Band A) 433 3 (Band B) 0.16 0.25 88 527 4 (Band A) 480 4 (Band B) 0.19 0.28 86 560 5 (Band A) 447 5 (Band B) 0.16 0.16 52 550 6 (Band A) 435 6 (Band B) 0.15 0.25 98 546 7 (Band A) 435 7 (Band B) 0.17 0.24 90 547 8 (Band A) 447 8 (Band B) 0.16 0.15 47 551 9 (Band A) 445 9 (Band B) 0.17 0.15 47 550 10 (Band A) 447 10 (Band B) 0.16 0.11 33 551 11 (Band A) 434 11 (Band B) 0.16 0.19 66 548 12 (Band A) 445 12 ( Band B) 0.17 0.07 63 541 13 (Band A) 430 13 (Band B) 0.13 0.23 153 533 14 (Band A) 480 14 (Band B) 0.1 5 0.34 148 543 15 (Band A) 441 15 (Band B) 0.10 0.05 24 546 17 (Band A) 430 17 (Band B) 0.09 0.04 44 536 18 (Band A) 441 18 (Band B) 0.16 0.10 39 535 CE1 (Band A) 422 CE2 (Band B) 0.18 0.22 56 518 [00175] The results in Table 1 show that the compounds of Examples 1-15, 17 and 18 demonstrated acceptable photochromic properties, for example sensitivity, saturation optical density and bleaching rate. A comparison of the data of the compounds of Examples 2, 5, 8, 9, 10, 12, 15 and 18 which have the same substituents as B and B 'as Comparative Example 1, for Comparative Example 1 shows a lambda Max plus high for both Bands A and B and a shorter bleaching rate for each of the compounds of the Example. Higher lambda Max values for the compounds of the Examples demonstrate a chromochromic trend in the visible spectrum. The present invention has been described with reference to specific details of particular embodiments thereof. Such details are not intended as limitations on the scope of the invention.

Claims (16)

Naphthopyran compound characterized in that it is represented by the following formula: wherein (a) R 1 and R 3) are each independently selected from hydrogen, C 1 -C 6 alkyl, unsubstituted phenyl and mono phenyl. -substituted, wherein each phenyl substituent is independently selected from (C 1 -C 6) alkoxy; (b) each R 3 is independently selected from hydrogen, C 1 -C 6 alkyl, C 1 -C 4 alkoxy, and (c) B and B 'are each independently selected from unsubstituted phenyl, monosubstituted phenyl and disubstituted phenyl where phenyl substituents are each independently selected from C1 -C4 alkyl; C1 -C6 alkoxy, morpholino and piperidino. 2. Naphthopyran compound characterized in that it is selected from: (a) 3,3,9-triferii la-3H-9H-indene (3 ', 2': 3,4)] in fto [1,2- (b) 3,3-di (4-methoxyphenyl) -9-phenyl-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b] pyran; c) 3- (4-methoxyphenyl) -3,9-diphenyl-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b] pyran; (d) 3- (4- morpholinephenyl) -3,9-diphenyl-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b] pyran; (e) 3,3-di (4-methoxyphenyl) -9 - (3-methoxyphenyl) -limide-3 H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b] pyran; (f) 3- (4-methoxyphenyl) - 3-phenyl-9- (3-methoxyphenyl) -1H-methoxy-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b] pyran; (g) 3- (4- methoxyphenyl) -3-phenyl-9-methyl-11-methoxy-9- (3-methoxyphenyl) -3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b] pyran; h) 3,3-di (4-methoxyphenyl) -9-methyl-11-methoxy-9- (3-methoxyphenyl) -3H-9H-indene [3 ', 2': 3,4] naphtho [1,2 (i) 3,3-di (4-methoxyphenyl) -9-methyl-11-methoxy-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b (j) 3,3-di (4-methoxyphenyl) -9,9-dimethyl-11-methoxy-3H-9H-indene [3 ', 2 ': 3,4] naphtho [1,2-b] pyran; (k) 3- (4-methoxyphenyl) -3-phenyl-9,9-dimethyl-11-methoxy-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b] pyran ; (1) 3,3-di (4-methoxyphenyl) -9,9-dimethyl-7,11-dimethoxy-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b] pyran; (m) 3- (4-methoxyphenyl) -3-phenyl-9,9-dimethyl-7,11-dimethoxy-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b ] pyran; (n) 3- (4-morpholinphenyl) -3-phenyl-9,9-dimethyl-7,11-dimethoxy-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b ] pyran; (o) 3,3-di (4-methoxyphenyl) -9-methyl-11,13-dimethoxy-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b] pyran; (p) 3- (4-Methoxyphenyl) -3-phenyl-9-methyl-11,13-dimethoxy-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b] pyran ; (q) 3- (4-methoxyphenyl) -3-phenyl-9,9-dimethyl-3H-9H-benzo [4 ", 5"] indene [3 ', 2': 3,4] naphtho [1,2 -b] pyran; and (r) 3,3-di (4-methoxyphenyl-9,9-dimethyl-11-fluoro-3H-9H-indene [3 ', 2': 3,4] naphtho [1,2-b] pyran. Photochromic article characterized in that it comprises a host organic polymeric material and a photochromic amount of the naphthopyran compound as defined in claim 1. Photochromic article according to claim 3, characterized in that the host organic polymeric material is selected from the group consisting of poly (C1-C12 alkyl methacrylates), poly (oxyalkylene dimethacrylates), poly (alkoxylated phenol methacrylates), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly (vinyl acetate), poly (vinyl alcohol), poly (vinyl chloride), poly (vinylidene chloride), thermoplastic polycarbonates, polyesters , polyurethanes, polythio urethanes, poly (ethylene terephthalate), polystyrene, poly (alpha methylstyrene), copoly (styrene methyl methacrylate), copoly (styrene acrylonitrile), polyvinyl butyral and polymers of the group consisting of bis (allyl carbonate) monomers ), polyfunctional acrylate monomers, polyfunctional methacrylate monomers, diethylene glycol dimethacrylate monomers, benzene diisopropenyl monomers, dime monomers ethoxylated tacrilate bisphenol A, ethylene glycol bismethacrylate monomers, poly (ethylene glycol) bismethacrylate monomers, phenol ethoxylated bismethacrylate monomers, polyhydric alcohol acrylate monomers, styrene monomers, urethanate acrylate monomers, glycidyl methacrylate monomers and diallylidene pentaerythritol monomers. Photochromic article according to claim 4, characterized in that the host organic polymeric material is a transparent solid polymer selected from the group consisting of poly (methyl methacrylate), poly (ethylene glycol bismethacrylate), poly (ethoxylated dimethacrylate) bisphenol A), thermoplastic polycarbonate, poly (vinyl acetate), polyvinyl butyral, polyurethane, polythiurethanes and group member polymers consisting of diethylene glycol bis (allyl carbonate) monomers, diethylene glycol dimethacrylate monomers, bismethacrylate monomers phenol ethoxylate, diisopropenyl benzene monomers, and trimethylol propane triacrylate monomers. Photochromic article according to claim 5, characterized in that the photochromic compound is present in an amount from 0.05 milligrams per square centimeter of a surface of a host organic material to which the photochromic substance (s) is incorporated. or is applied. Photochromic article according to claim 6, characterized in that said article is a lens. A photochromic article comprising a polymerised product of a monomer of an organic optical resin and a photochromic amount of the naphthopyran compound as defined in claim 1. Photochromic article according to claim 8, characterized in that the refractive index of the polymerized product is from approximately 1.48 to approximately 1.75. Photochromic article according to claim 8, characterized in that the polymerized product is an optical element. Photochromic article according to claim 10, characterized in that said optical element is an ophthalmic lens or a contact lens. Photochromic article characterized in that it comprises, in combination, a transparent solid host organic polymeric material, and a photochromic amount of each of: (a) a naphthalopyran compound as defined in claim 1; and (b) another photochromic organic compound having at least a maximum activated absorption within a range of approximately 400 to 700 nanometers. Photochromic article according to claim 12, characterized in that the host organic polymeric material is a copolymer or a transparent solid homopolymer selected from the group consisting of poly (methyl methacrylate), poly (ethylene bis-methacrylate). glycol), bisphenol A ethoxylated poly (dimethacrylate), thermoplastic polycarbonate, polyvinyl acetate, polyvinyl butyral, polyurethane, polythiurethane and group member polymers consisting of diethylene glycol bis (allyl carbonate) monomers, diethylene glycol dimethacrylate, phenol ethoxylated bismethacrylate monomers, benzene diisopropenyl monomers and trimethylol ethoxylated propane triacrylate monomers. Photochromic article according to claim 13, characterized in that the photochromic organic compound (b) is selected from the group consisting of naphthopyran, benzopyran, phenanthropyrane, indenonaptopyrane, oxazine, fulgido, fulgimide , spiro (indoline) pyranes and mixtures thereof. Photochromic article according to claim 14, characterized in that the total amount of photochromic compound present is from 0.05 to 1.0 milligrams per square centimeter of the host organic surface material on which the substance (s) ) photochromic is incorporated or applied. Photochromic article according to claim 15, characterized in that the article is an ophthalmic lens or a contact lens.